CN102315441B - Positive active material, the method manufacturing this positive active material and lithium secondary battery - Google Patents

Positive active material, the method manufacturing this positive active material and lithium secondary battery Download PDF

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CN102315441B
CN102315441B CN201110191933.XA CN201110191933A CN102315441B CN 102315441 B CN102315441 B CN 102315441B CN 201110191933 A CN201110191933 A CN 201110191933A CN 102315441 B CN102315441 B CN 102315441B
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active material
lithium
positive active
secondary battery
positive
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CN102315441A (en
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宋在爀
李泳勋
宋有美
金荣基
李淳律
崔益圭
金润昶
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Samsung SDI Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention provides a kind of positive active material for lithium secondary battery, comprise the compound containing lithium aluminum oxide and lithium nickel oxide, and manufacture the method for described positive active material, and use the lithium secondary battery of this positive active material.

Description

Positive active material, the method manufacturing this positive active material and lithium secondary battery
Technical field
One or more execution mode relate to for lithium secondary battery positive active material and use the lithium secondary battery of this material.
Background technology
Lithium secondary battery as portable electronic devices power supply is noticeable recently, and wherein lithium secondary battery uses organic electrolyte, and therefore its discharge voltage had is 2 times that use standard aqueous alkali lye battery, therefore has high-energy-density.
Lithium secondary battery by can embed or de-embedding lithium ion material be used as negative pole and positive pole, and electrolyte is added between positive pole and negative pole and prepares, and by embed at positive pole and negative pole place and de-embedding lithium ion time generation oxidation reaction and reduction reaction produce electric energy.
Carbon class material is used as the electrode active material forming lithium secondary battery anode.
On the other hand, if change carbon class material into silica type material, the performance of lithium secondary battery can be improved.But, due to can irreversibility be there is in silica type material, so silica type material can absorb lithium ion when first time charging, do not discharge at the lithium ion of interdischarge interval about 20% thereafter.Therefore, in first time charging, the positive active material of used about 20% can not participate in charging and discharging after first time charging, and therefore the performance of battery can worsen.
Therefore, the positive electrode added in the battery of per unit weight or volume containing a large amount of lithium Li has been advised.But this positive electrode produces gas between charge period, therefore the stability of battery can worsen.
Summary of the invention
One or more execution mode comprises a kind of positive active material for lithium secondary battery and uses the lithium secondary battery of described positive active material, and the gas in described positive active material between charge period produces suppressed.
Embodiment there is provided a kind of positive active material for lithium secondary battery according to one or more, comprise the compound containing the lithium aluminum oxide shown in following general formula 1 and lithium nickel oxide.
[general formula 1]
Li aAl xO b
In general formula 1, a is the number of about 0.1 to about 5.5, and x is the number of about 1 to about 5, and b is the number of about 1.5 to about 8.
The described positive active material for lithium secondary battery can comprise lithium transition-metal oxide further.
Embodiment there is provided a kind of lithium secondary battery according to one or more, the dividing plate comprising positive pole, negative pole and be inserted between described positive pole and described negative pole, wherein said positive pole comprises the described positive active material for lithium secondary battery.
According to one or more a kind of method that embodiment there is provided positive active material for the preparation of lithium secondary battery, comprising: mixing oxidate for lithium, nickel oxide and aluminum precursor are to produce mixture; The compound forming lithium nickel oxide and lithium aluminum oxide is heat-treated with to described mixture.
For in the positive active material of lithium secondary battery, the gas under recharge and discharging condition can be suppressed to produce.Therefore, the lithium secondary battery of the reliability and stability with improvement can be manufactured.
Accompanying drawing explanation
Fig. 1 is the figure of the lithium secondary battery according to an execution mode; And
Fig. 2 is the figure of the X-ray diffraction analysis of the positive active material that display is prepared according to synthesis example 1.
Embodiment
Positive active material for lithium secondary battery comprises the compound containing the lithium aluminum oxide shown in following general formula 1 and lithium nickel oxide.
General formula 1
Li aAl xO b
In general formula 1, a is the number of about 0.1 to about 5.5, and x is the number of about 1 to about 5, and b is the number of about 1.5 to about 8.
Lithium nickel oxide can be Li 2niO 2.
Lithium aluminum oxide can be Li 5alO 4, LiAlO 2or LiAl 5o 8.
Lithium aluminum oxide can comprise and being selected from by Li 5alO 4, LiAlO 2, LiAl 5o 8with at least one in the group that its mixture forms.
Based on the lithium nickel oxide of 100 weight portions, the content of described lithium aluminum oxide can be about 15 to about 100 weight portions.
If lithium aluminum oxide and lithium nickel oxide (Li 2niO 2) weight ratio in above-mentioned scope, the reliability and stability of the battery that can effectively suppress the carbon dioxide produced because of unreacted oxidate for lithium to cause worsen, and can improve the capacity of battery.
The method that be used for the positive active material of lithium secondary battery of preparation according to an execution mode will be described below.
First, be mixed with each other oxidate for lithium, nickel oxide and aluminum precursor also heat treatment.
Oxidate for lithium can be Li 2o, and nickel oxide can be NiO.
Aluminum precursor is the parent material for the formation of compound, and can be gama-alumina (Al 2o 3), aluminium hydroxide (Al (OH) 3) etc.
Based on the oxidate for lithium of 1 mole, the content of nickel oxide can be about 0.4 to about 2 mole, such as 0.8 to 1.2 mole, and based on the oxidate for lithium of 1 mole, the amount of aluminum precursor can be about 0.01 to about 0.5 mole, such as 0.1 to 0.4 mole.
If the content of nickel oxide and aluminum precursor is in above-mentioned scope, the capacity of battery can not worsen, and can improve the suppression generated gas.
Heat treatment can comprise solid-state reaction and can carry out at the temperature of about 500 to about 700 DEG C.If heat treatment is carried out in above-mentioned scope, the capacity of final positive active material can be improved.
The heat treated time according to heat treated variations in temperature, and can be about 5 to about 24 hours.
Heat treatment can be carried out under an inert atmosphere.Inert gas such as nitrogen or argon gas can be used in an inert atmosphere.
In the positive active material as above prepared, CuK-α characteristic x-ray wavelength the main peak of Larger bragg angles 2 θ at least appear between 25 ° and 28 °.
Main peak between 25 ° and 28 ° is Li 2niO 2peak.Except main peak, Li 5alO 4peak appear between about 32 ° and about 35 °.
According to above-mentioned preparation method, when by Li 2niO 2during as positive active material, according to following reaction equation 1, unreacted oxidate for lithium (Li 2o) lithium carbonate (Li is become 2cO 3).Therefore, when assembled battery, as shown in following reaction equation 2, carbon dioxide can be produced in battery.For the formation of Li aalO baluminum precursor and unreacted lithia between can react, and the material with the phase not producing carbon dioxide can be formed thus.The material with the phase not producing carbon dioxide can be Li 5alO 4, LiAlO 2or LiAl 5o 8.
Reaction equation 1
Li 2O→Li 2CO 3
Reaction equation 2
Li 2CO 3→Li 2O+CO 2
For in the positive active material of lithium secondary battery, can at 4.5 volts or lower, suppress gas to produce under the battery-operated voltage band of 3.5 to about 4.5 volts according to appointment.
The capacity of the positive active material for lithium secondary battery of per unit weight is 350mAh/g or higher, and 350 to about 500mAh/g according to appointment, is therefore improved.
The positive active material for lithium secondary battery mixed with at least one lithium transition-metal oxide can be used.
The example of lithium transition-metal oxide can comprise and being selected from by LiCoO 2, LiNiO 2, LiMnO 2, LiMn 2o 4, Li (Ni aco bmn c) O 2(0 < a < 1,0 < b < 1,0 < c < 1, a+b+c=1), LiNi 1-Yco yo 2(herein, 0≤Y < 1), LiCo 1-Ymn yo 2(herein, 0≤Y < 1), LiNi 1-Ymn yo 2(herein, 0≤Y < 1), Li (Ni aco bmn c) O 4(0 < a < 2,0 < b < 2,0 < c < 2, a+b+c=2), LiMn 2-zni zo 4(herein, 0 < Z < 2), LiMn 2-zco zo 4(herein, 0 < Z < 2), LiCoPO 4and LiFePO 4at least one in the group of composition.
According to an execution mode, lithium transition-metal oxide can comprise as LiCoO 2.
Based on the lithium transition-metal oxide of 100 weight portions, lithium nickel oxide (Li 2niO 2) content can be about 0.1 to about 20 weight portion, 8 to about 12 weight portions according to appointment.
If when the content of lithium nickel oxide is in above-mentioned scope, when repeating charging and discharging, gas can be effectively suppressed to produce and do not reduce capacity.
Positive active material according to an execution mode can be Li 5alO 4and Li 2niO 2compound.
At Li 5alO 4and Li 2niO 2compound in, based on the Li of 100 weight portions 2niO 2, Li 5alO 4content can be about 1 to about 30 weight portion, 5 to about 15 weight portions according to appointment.
When the positive active material according to execution mode is selected from by Li for comprising 5alO 4, LiAlO 2and LiAl 5o 8a kind of, Li in the group of composition 2niO 2and LiCoO 2compound time, based on the LiCoO of 100 weight portions 2, Li 2niO 2content can be about 0.1 to about 20 weight portion, 8 to about 12 weight portions according to appointment.
According to an execution mode, based on the Li of 100 weight portions 2niO 2, be selected from by Li 5alO 4, LiAlO 2and LiAl 5o 8in the group of composition, a kind of content can be about 1 to about 30 weight portion, 5 to about 15 weight portions according to appointment.
According to an execution mode, the average diameter comprising the positive active material of this compound can be about 1 to about 30 μm, 3 to about 7 μm according to appointment.If the average diameter of positive active material is in above-mentioned scope, improve the capacity of battery.
Hereinafter, will describe the method manufacturing lithium secondary battery with the above-mentioned negative electrode active material for lithium secondary battery, wherein lithium secondary battery comprises positive pole, negative pole, electrolyte and dividing plate.
Positive pole and negative pole are by being coated with the composition for the formation of positive active material and the composition for the formation of negative electrode active material on a current collector respectively, and drying is formed through the composition of coating on this collector.
For the formation of the composition of positive active material by compound, conductive agent, binding agent and solvent being prepared, described compound is positive active material.
Positive active material can comprise the lithium transition-metal oxide being typically used as positive active material in lithium secondary battery.
Binding agent is for active material and the conductive agent of boning, and to collector bonding active material, and based on the positive active material of 100 weight portions, the content of binding agent can be about 1 to about 50 weight portion, according to appointment 10 to about 15 weight portions.If when the content of binding agent is in above-mentioned scope, the adhesion strength between collector and active material improves.
The example of binding agent can include but not limited to the EPDM of polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, PVP, tetrafluoroethene, polyethylene, polypropylene, Ethylene-Propylene-Diene trimer (EPDM), semi-annular jade pendant, styrene butadiene ribber, fluorine-containing rubber (fluorrubber) and various copolymer.
Only otherwise cause the chemical change in battery and have conductivity, conductive agent is not particularly limited.The example of conductive agent comprises graphite as native graphite or Delanium; Carbon black is as carbon black, acetylene black, Ketjen black, channel black, furnace black or dim; Conductive fiber is as carbon fiber or metallic fiber; Metal powder is as aluminium or nickel powder; Conductive whiskers is as zinc oxide or potassium titanate; Conductive oxide is as titanium oxide; With conducting organic material as polypheny lene derivatives.Based on the positive active material of 100 weight portions, the content of conductive agent can be about 2 to about 30 weight portions, according to appointment 10 to about 15 weight portions.If the content of conductive agent is in above-mentioned scope, the conductance of the final electrode obtained is enhanced, and can keep the capacity of battery.
Solvent can be METHYLPYRROLIDONE.Based on the positive active material of 100 weight portions, the content of solvent can be about 100 to about 400 weight portions.If the content of solvent is in above-mentioned scope, be easy to form active material layer.
Positive collector can have the thickness of about 3 to about 500 μm and be not particularly limited, as long as it does not cause chemical change and has high conductivity in the battery of these execution modes.The example of positive collector can comprise stainless steel, aluminium, nickel, titanium, plasticizing carbon, or treated carbon, nickel, titanium, plasticizing carbon or silver on aluminium or stainless steel surfaces.Process the surface of positive collector unevenly, thus improve the bonding strength of positive active material.The example of positive collector can comprise film, plate, paper tinsel, net, porous material, trellis (form) and non-woven material.
Can individually by negative electrode active material, binding agent, conductive agent and solvent with for the preparation of forming the composition of negative electrode active material.
Negative electrode active material can comprise carbon class material as graphite, carbon, and lithium metal maybe can embed or the alloy of de-embedding lithium ion, and silica type material.
Binding agent is for active material and the conductive agent of boning, and to collector bonding active material, and based on the negative electrode active material of 100 weight portions, the content of binding agent can be about 1 to about 50 weight portion, according to appointment 10 to about 15 weight portions.Binding agent can be and forms the identical material of middle types of binder with positive pole.
Based on the negative electrode active material of 100 weight portions, the content of conductive agent can be about 2 to about 30 weight portions, according to appointment 10 to about 15 weight portions.If the content of conductive agent is in above-mentioned scope, the conductance of the final electrode obtained is enhanced.
Based on the negative electrode active material of 100 weight portions, the content of solvent can be about 80 to about 400 weight portions.If the content of solvent is in above-mentioned scope, can be easy to form active material layer.
Conductive agent and solvent can be and form the middle conductive agent material identical with solvent with positive pole.
Negative collector can have the thickness of about 3 to about 500 μm and be not particularly limited, as long as it does not cause chemical change and has high conductivity in the battery of embodiment of the present invention.The example of negative collector can comprise copper; Stainless steel; Aluminium; Nickel; Plasticizing carbon; Treated carbon, nickel, titanium or silver on copper or stainless steel surfaces; Aluminium-cadmium alloy.In addition, similar with positive collector, thin roughness can be formed on negative collector, thus improve the bonding strength of negative electrode active material.The example of negative collector can comprise film, plate, paper tinsel, net, porous material, trellis (form) and non-woven material.
Dividing plate can insert between a positive electrode and a negative electrode to form battery component.By battery component winding or folding, be sealed in subsequently in cylinder or rectangular battery shell.Subsequently, organic electrolyte is injected battery case, to complete the manufacture of lithium ion battery.Or according to an execution mode, multiple electrode assemblie can be stacked in two cellular construction, and pours into organic electrolyte.Gains put into bag and seals, thus completing the manufacture of lithium ion polymer battery.
Fig. 1 is the decomposition diagram of the lithium secondary battery according to an execution mode.With reference to Fig. 1, lithium secondary battery 30 according to the present embodiment comprises containing the positive pole 23 of positive active material, negative pole 22 and the dividing plate 24 that is inserted between positive pole 23 and negative pole 24, and injects the electrolyte (not shown) of positive pole 23, negative pole 22 and dividing plate 24, battery case 25 and the potted component 26 for capsul 25.By positive pole 23, negative pole 22 and dividing plate 24 is on the other stacking according to next, reel this stacking material in a spiral form, and prepare lithium secondary battery 30 by the stacking material of winding insertion battery case 25.
Dividing plate can have the aperture of about 0.1 to about 10 μm and the thickness of about 5 to about 300 μm.Dividing plate can have the form of plate or nonwoven fabrics, and can by polyolefin as polyethylene or polypropylene or glass fibre are formed.When polymer dielectric is used as above-mentioned electrolyte, dividing plate can use together.
Electrolyte can be formed by non-aqueous organic solvent and lithium salts.
Non-aqueous organic solvent should comprise linear carbonate and cyclic carbonate.
The example of linear carbonate comprises dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), diethyl carbonate (DEC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC), ethyl propyl carbonic acid ester (EPC) etc.
The example of cyclic carbonate comprises ethylene carbonate (EC), propylene carbonate (PC) etc.
Based on the non-aqueous organic solvent of 100 parts by volume, the total amount of linear carbonate can in the scope of about 50 to about 90 parts by volume.
Non-aqueous organic solvent can comprise at least one first material in the group being selected from and being made up of ester solvent, ether solvents, ketone solvent, alcoholic solvent and aprotic solvent further.
Ester solvent can be methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate (diethylacetate), methyl propionate, ethyl propionate, gamma-butyrolacton, decalactone, valerolactone, mevalonolactone, caprolactone etc., but is not limited thereto.
Ether solvents can be butyl oxide, tetraethyleneglycol dimethyl ether, diethylene glycol dimethyl ether, dimethoxy-ethane, 2-methyltetrahydrofuran, oxolane etc., but is not limited thereto.
Ketone solvent can be cyclohexanone, but is not limited thereto.
Alcoholic solvent can be ethanol, isopropyl alcohol etc., but is not limited thereto.
Aprotic solvent can be nitrile, and as R-CN, (wherein R is C 2-C 20straight chain, side chain or cyclic hydrocarbon group, it can comprise double bond aromatic ring or ehter bond), acid amides, as dimethyl formamide; Dioxolane, as 1,3-dioxolane; Sulfolane etc., but be not limited thereto.
The example of non-aqueous organic solvent comprises ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC).Such as, non-aqueous organic solvent can be volume ratio the be ethylene carbonate (EC) of 1: 1: 1, the mixture of methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC), but be not limited thereto.
The lithium salts comprised in electrolyte is dissolved in non-aqueous organic solvent, and plays the effect of lithium ion source in lithium secondary battery, to make lithium secondary battery run, and promotes that the lithium ion between positive pole and negative pole moves.
Such as, lithium salts can comprise and being selected from by LiPF 6, LiBF 4, LiSbF 6, LiAsF 6, LiN (SO 2c 2f 5) 2, Li (CF 3sO 2) 2n, LiC 4f 9sO 3, LiClO 4, LiAlO 2, LiAlCl 4, LiN (C xf 2x+1sO 2) (C yf 2y+1sO 2) (wherein x and y is natural number independently of one another), LiCl, LiI and two (oxalic acid) lithium borate (LiB (C 2o 4) 2) the supportive electrolytic salt of at least one in the group that forms.
The concentration of lithium salts can be about 0.1M to about 2.0M, according to appointment 0.6M to about 2.0M.The concentration of lithium salts can be about 0.7M to about 1.0M.When the concentration of lithium salts is in above-mentioned scope, electrolyte can have required conductance and viscosity, and therefore lithium ion can move effectively.
Hereinafter, with reference to following examples, each execution mode is described in more detail; But these execution modes are not limited to following embodiment.
synthesis example 1: comprise containing Li 5 alO 4 and Li 2 niO 2 the preparation of positive active material of compound
By Li 2o and NiO as raw material with 1.05: 1 mol ratio be mixed with each other to prepare mixture, by the Li based on 100 moles 2o is the γ-Al of 20 moles 2o 3to add in mixture and to mix with mechanical mixer.
By gains at inertia N 2heat treatment about 10 hours at atmosphere and about 550 DEG C.Now, temperature rising and cooling rate are set as 2 DEG C/min, thus preparation comprises containing Li 5alO 4and Li 2niO 2the positive active material of compound.In the positive active material prepared according to synthesis example 1, Li 5alO 4and Li 2niO 2mixed weight ratio be 32: 68.
Analyze the X ray diffracting characteristic of the positive active material prepared according to synthesis example 1, and result display in FIG.
The X-ray spectrometer that X-ray diffraction analysis uses PANalytical to manufacture carries out under the following conditions: scanning area: 15-70 °, sweep spacing: 0.05 °, and sweep speed: 1 time/0.5 second.
With reference to Fig. 1, visible Li 5alO 4and Li 2niO 2coexist.
synthesis example 2: comprise containing Li 5 alO 4 and Li 2 niO 2 the preparation of positive active material of compound
The employing mode identical with synthesis example 1 prepares the Li containing 19: 81 mixed weight ratios 5alO 4and Li 2niO 2positive active material, difference be based on 100 moles of Li 2o, γ-Al 2o 3content be 10 moles.
synthesis example 3: comprise containing Li 5 alO 4 and Li 2 niO 2 the preparation of positive active material of compound
The employing mode identical with synthesis example 1 prepares the Li containing 42: 58 mixed weight ratios 5alO 4and Li 2niO 2positive active material, difference be based on 100 moles of Li 2o, γ-Al 2o 3content be 30 moles.
synthesis example 4: comprise containing Li 5 alO 4 and Li 2 niO 2 the preparation of positive active material of compound
The employing mode identical with synthesis example 1 prepares the Li containing 49: 51 mixed weight ratios 5alO 4and Li 2niO 2positive active material, difference be based on 100 moles of Li 2o, γ-Al 2o 3content be 40 moles.
embodiment 1: the preparation of positive pole and use the battery of this positive pole
By with comprising containing Li of preparing according to synthesis example 1 5alO 4and Li 2niO 2the positive active material of compound prepare positive half-cell.
By weight ratio be the positive active material of 90: 5: 5, polyvinylidene fluoride and black dispersion in 1-METHYLPYRROLIDONE to prepare anode sizing agent.
Anode sizing agent is coated on the thickness with about 60 μm on aluminium film, to prepare thin pole plate, and by this thin pole plate at about 135 DEG C dry 3 hours or longer and extrude, thus prepares positive pole.
Negative pole can comprise lithium (Li) metal.
Electrolyte passes through 1.3MLiPF 6join in the solvent obtained with 1: 1: 1 volume ratio mixed carbonic acid ethyl (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DEC) and prepare.
The dividing plate formed by porous polyethylene (PE) can be inserted between positive pole and negative pole to form electrode assemblie.By this electrode assemblie winding or extruding, be sealed in subsequently in battery case.Subsequently, organic electrolyte is injected battery case, to complete the manufacture of positive half-cell.
embodiment 2-4: the preparation of the battery of positive pole and this positive pole of use
Adopt the mode identical with embodiment 1 to prepare positive half-cell, difference is to use comprising containing Li according to synthesis example 2 to 4 preparation respectively 5alO 4and Li 2niO 2the positive active material of compound, to substitute comprising containing Li of preparing according to synthesis example 1 5alO 4and Li 2niO 2the positive active material of compound.
comparative example 1: the preparation of the battery of positive pole and this positive pole of use
Adopt the mode identical with embodiment 1 to prepare positive half-cell, difference is Li 2niO 2as positive active material, with substitute according to synthesis example 1 prepare containing Li 5alO 4and Li 2niO 2positive active material.
In the positive half-cell prepared according to embodiment 1 to 4 and comparative example 1, calculate gas generated and unit capacity gas generated of the weight of positive active material, charging capacity, gas generated, Unit Weight respectively, and result display in table 1 below.
comparative example 2: the preparation of the battery of positive pole and this positive pole of use
Adopt the mode identical with embodiment 1 to prepare positive half-cell, difference is that by mixed weight ratio be the Li of 32: 68 5alO 4and Li 2niO 2mixture be used as positive active material, with substitute according to synthesis example 1 prepare comprising containing Li 5alO 4and Li 2niO 2the positive active material of compound.
comparative example 3: the preparation of the battery of positive pole and this positive pole of use
Adopt the mode identical with embodiment 1 to prepare positive half-cell, difference is that by mixed weight ratio be the Li of 19: 81 5alO 4and Li 2niO 2mixture be used as positive active material, with substitute according to synthesis example 1 prepare comprising containing Li 5alO 4and Li 2niO 2the positive active material of compound.
Gas generated by use bag as the battery case in embodiment 1 to 4 and collect battery charging time produce gas evaluate.Gas generated and the unit capacity of Unit Weight gas generated by evaluating with the capacity of the gas generated weight divided by positive active material and respective battery.
[table 1]
According to table 1, compared with the positive half-cell of comparative example 1 to 3, the positive half-cell of embodiment 1 to 4 can suppress Li effectively 2niO 2gas produce.
Illustrative embodiments described herein should be understood should only illustratively understand, and be not used in the object of restriction.Feature in each execution mode or the description of aspect should be considered to can be used for other similar characteristics in other execution mode or aspect usually.

Claims (11)

1. for a positive active material for lithium secondary battery, comprise the compound of lithium nickel oxide and lithium aluminum oxide, wherein said lithium aluminum oxide is by shown in general formula 1, and wherein said lithium nickel oxide is Li 2niO 2;
General formula 1
Li aAl xO b；
Wherein a is 0.1 to 5.5;
X is 1 to 5; And
B is 1.5 to 8,
Wherein, based on the described lithium nickel oxide of 100 weight portions, the content of described lithium aluminum oxide is 15 to 100 weight portions.
2. positive active material as claimed in claim 1, comprises lithium transition-metal oxide further.
3. positive active material as claimed in claim 1, wherein said lithium aluminum oxide comprises Li 5alO 4, LiAlO 2, LiAl 5o 8with at least one in their mixture.
4. positive active material as claimed in claim 1, the CuK-α characteristic x-ray wavelength of wherein said positive active material the main peak of Larger bragg angles 2 θ at least appear between 25 ° and 28 °, and the CuK-α characteristic x-ray wavelength of described positive active material other peak of Larger bragg angles 2 θ appear between 32 ° and 35 °.
5. positive active material as claimed in claim 2, wherein based on the described lithium transition-metal oxide of 100 weight portions, the content of described lithium nickel oxide is 0.1 to 20 weight portion.
6. a lithium secondary battery, comprising:
Positive pole,
Negative pole,
And the dividing plate be inserted between described positive pole and described negative pole,
Wherein, described positive pole comprises the positive active material in claim 1 to 5 described in any one.
7., for the preparation of a method for the positive active material of lithium secondary battery, comprising:
Mixing oxidate for lithium, nickel oxide and aluminum precursor are to produce mixture; With
Heat-treat to described mixture the compound forming lithium nickel oxide and lithium aluminum oxide, wherein said lithium aluminum oxide is by shown in general formula 1, and wherein said lithium nickel oxide is Li 2niO 2;
General formula 1
Li aAl xO b；
Wherein a is 0.1 to 5.5;
X is 1 to 5; And
B is 1.5 to 8,
Wherein, based on the described oxidate for lithium of 1 mole, the content of nickel oxide described in described mixture is 0.4 mole to 2 moles, and based on the described oxidate for lithium of 1 mole, the content of described aluminum precursor is 0.01 mole to 0.5 mole.
8., as claimed in claim 7 for the preparation of the method for the positive active material of lithium secondary battery, wherein said oxidate for lithium is Li 2o, and described nickel oxide is NiO.
9., as claimed in claim 7 for the preparation of the method for the positive active material of lithium secondary battery, wherein said aluminum precursor is for being selected from by γ-Al 2o 3with Al (OH) 3at least one in the group of composition.
10., as claimed in claim 7 for the preparation of the method for the positive active material of lithium secondary battery, wherein said heat treatment is carried out at the temperature of 500 DEG C to 700 DEG C and inert atmosphere.
11. as claimed in claim 7 for the preparation of the methods of the positive active material of lithium secondary battery, comprise the step joined by lithium transition-metal oxide in described mixture further.
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